π‐Interpenetrated 3D Covalent Organic Frameworks from Distorted Polycyclic Aromatic Hydrocarbons

Martínez‐Abadía, Marta; Strutyński, Karol; Lerma‐Berlanga, Belén; Stoppiello, Craig T.; Khlobystov, Andrei N.; Martí‐Gastaldo, Carlos; Saeki, Akinori; Melle‐Franco, Manuel; Mateo‐Alonso, Aurelio

doi:10.1002/ange.202100434

Cited by 13 publications

(7 citation statements)

References 66 publications

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“…[29] In principle, more novel frameworks in 3D COFs, such as zeolite-like networks, could be also created by tetrahedral moieties as interlinked centers rather than just a limited number of topologies, e.g., dia, ctn, bor, and pts. [30][31][32][33][34][35][36][37] However, this avenue has not yet been explored.…”

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confidence: 99%

Design and Synthesis of a Zeolitic Organic Framework**

et al. 2022

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The development of novel zeolite‐like materials with large channel windows and high stability is of importance but remains a tremendous challenge. Herein, we report the first example of a 3D covalent organic framework with zeolitic network, namely the zeolitic organic framework (ZOF). By combining two kinds of tetrahedral building blocks with fixed or relatively free bond angles, ZOF‐1 with the zeolitic crb net has been successfully synthesized. Its structure was determined by the single‐crystal 3D electron diffraction technique. Remarkably, ZOF‐1 shows high chemical stability, large pore size (up to 16 Å), and excellent specific surface area (≈2785 m2 g−1), which is superior to its analogues with the same network, including traditional aluminosilicate zeolites and zeolitic imidazole frameworks. This study thus opens a new avenue to construct zeolite‐like materials with pure organic frameworks and will promote their potential applications in adsorption and catalysis for macromolecules.

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confidence: 99%

Design and Synthesis of a Zeolitic Organic Framework**

et al. 2022

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“…The theoretical specific surface area of two‐dimensional (2D) COFs is usually 2000–3000 m 2 g −1 , the theoretical limitation of 3D COFs could be as high as 7000–10 000 m 2 g −1 25 . However, the usually obtained surface area of 3D COFs was significantly lower than theoretical value, resulting from the widely observed crystallinity issue and interpenetration phenomena 26–31 . Currently, methods to reduce the interpenetration are focused on: (1) shortening the length of the linkers, 32 (2) increasing the steric hindrance, 33 (3) controlling reaction conditions, 27,31 and (4) increasing the repulsive effect of the linkers 34 .…”

Section: Introductionmentioning

confidence: 99%

“…25 However, the usually obtained surface area of 3D COFs was significantly lower than theoretical value, resulting from the widely observed crystallinity issue and interpenetration phenomena. [26][27][28][29][30][31] Currently, methods to reduce the interpenetration are focused on: (1) shortening the length of the linkers, 32 (2) increasing the steric hindrance, 33 (3) controlling reaction conditions, 27,31 and (4) increasing the repulsive effect of the linkers. 34 Herein, we selected the bor topology that rarely occurs interpenetration phenomenon to prepare mesoporous imine-linked 3D COFs.…”

Section: Introductionmentioning

confidence: 99%

Rational design of imine‐linked three‐dimensional mesoporous covalent organic frameworks with bor topology

Hsueh

Tang

et al. 2022

SusMat

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Three-dimensional (3D) covalent organic frameworks (COFs) possess great potential applications in various fields. Constructing 3D COFs with large pore sizes is extremely challenging due to the interpenetration and collapse. Herein, we report a series of crystalline imine-linked 3D COFs (3D-bor-COF-1, 3D-bor-COF-2, 3D-bor-COF-3) with mesoporous channels through rationally designing the topology configuration. These 3D-bor-COFs display permanent porosity and Brunauer-Emmett-Teller (BET) surfaces of 3205.5, 1752.7, and 2077.3 m 2 g −1 (S Langmuir = 4277.7, 2480.3, and 2698.0 m 2 g −1 ), respectively. The pore sizes of 3Dbor-COFs were confirmed by the lattice fringes from high-resolution transmission electron microscopy, as well as structural simulation and nitrogen adsorption isotherm analysis. 3D-bor-COFs display large pore sizes (3.8 nm for 3D-bor-COF-3), which is among the highest record of 3D COFs. Owing to the unstackedaromatic pore environment and high specific surface area, 3D-bor-COFs display excellent adsorption capacity for benzene vapor (1203.9 mg g −1 for 3D-bor-COF-3) under 298 K, which is three times higher than that of the best-reported 2D COF. This work not only provides inspiration for designing 3D mesoporous imine-COFs, but also demonstrates a strategy for constructing aromatics adsorption materials.

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“…Different from triangular prismatic (D3h) nodes, Mateo-Alonso et al utilized triangular antiprismatic (D3d) nodes to construct pcu topology 3D COFs. 51 Other unprecedented 3D COF topologies reported are ffc, 52 srs, 53 fjh, 54 tbo, 55 and nbo 56 . Recently, octatopic nodes have been used to prepare pcb 57 and bcu 58 topology 3D COFs.…”

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confidence: 99%

Three-Dimensional Covalent Organic Frameworks with scu Topology

Sekine

Mabuchi

et al. 2022

Preprint

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Three-dimensional (3D) covalent organic frameworks (COFs) exemplify a new generation of crystalline extended solids with intriguing structures and unprecedented porosity. Notwithstanding substantial scope, the reticular synthesis of 3D COFs from pre-designed building units leading to new network topologies yet remains a demanding task owing to the shortage of 3D building units and inadequate reversibility of the linkages between the building units. In this work, by linking a tetragonal prism (8-connected) node with a square planar (4-connected) node, we report the first 3D COF with scu topology. The new COF, namely TUS-84, features a two-fold interpenetrated structure with well-defined porosity and a Brunauer−Emmett−Teller surface area of 679 m2 g-1. In drug delivery applications, TUS-84 shows efficient drug loading and sus-tained release profile.

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π‐Interpenetrated 3D Covalent Organic Frameworks from Distorted Polycyclic Aromatic Hydrocarbons

Cited by 13 publications

References 66 publications

Design and Synthesis of a Zeolitic Organic Framework**

Design and Synthesis of a Zeolitic Organic Framework**

Rational design of imine‐linked three‐dimensional mesoporous covalent organic frameworks with bor topology

Three-Dimensional Covalent Organic Frameworks with scu Topology

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